Pigment preparation

ABSTRACT

Process for preparing pigments by applying a polymerizable mixture to a surface, orienting the liquid crystals present in the mixture, polymerizing the mixture, detaching the polymer film from the surface and comminuting the polymer film to form pigment particles, wherein the polymerizable mixture comprises: 
     a 1 ) at least one chiral liquid-crystalline polymerizable monomer or 
     a 2 ) at least one achiral liquid-crystalline polymerizable monomer and a chiral compound, and additionally 
     b) a polymeric binder and/or monomeric compounds which are converted by polymerization into a polymeric binder and/or a dispersion auxiliary.

The present invention relates to a process for preparing pigments byapplying a polymerizable mixture to a surface, orienting the liquidcrystals present in the mixture, polymerizing the mixture, detaching thepolymer film from the surface and comminuting the polymer film to formpigment particles, wherein the polymerizable mixture comprises:

a₁) at least one chiral liquid-crystalline polymerizable monomer or

a₂) at least one achiral liquid-crystalline polymerizable monomer and achiral compound, and additionally

b) a polymeric binder and/or monomeric compounds which are converted bypolymerization into a polymeric binder and/or a dispersion auxiliary.

The present invention additionally relates to pigments obtainable bythis process, to coating compositions comprising these pigments, to theuse of the pigments in emulsion paints and other surface coatings, tothe use of the coating compositions comprising the pigments for coatingcommodity articles, especially vehicles, and to vehicles coated withthese coating compositions.

Pigments having a cholesteric liquid-crystalline structure are ofinterest as special-effect pigments whose perceived color depends on theviewing angle. The perceived color arises through interference effectsin a helical superstructure which is an essential feature of thecholesteric liquid-crystalline phase.

Pigments whose color depends on the viewing angle, which consist oforiented three-dimensionally crosslinked substances ofliquid-crystalline structure with a chiral phase, and if desired offurther dyes and pigments, are known from EP-B1-0 601 483. However, thebrightness of color of these pigments is not fully satisfactory.

Prior German Patent Application 19 532 419.6 describes a process for thesurface coating of substrates, in which the coating compositioncomprises liquid-crystalline polymerizable monomers, with or withoutchiral compounds which induce a cholesteric structure, and, in addition,a polymeric binder and/or monomeric compounds which can be convertedinto the polymeric binder by polymerization, or a dispersion auxiliary.These polymeric binders and dispersion auxiliaries facilitate theorientation of the liquid-crystalline compounds and enable spontaneousorientation to form the cholesteric liquid-crystalline phase merely bymeans of the coating operation.

It is an object of the present invention to discover a process forpreparing pigments whose color depends on the viewing angle and whichare particularly bright in color.

We have found that this object is achieved by the pigment preparationprocess described at the outset.

The novel process starts from a polymerizable mixture. Polymerizable inthis context means that the monomers present in the mixture can beconverted into polymers by various upbuilding reactions, for examplechain addition polymerization, stepwise addition polymerization orcondensation polymerization.

The polymerizable mixture is first of all applied to a surface,preferably a film or a rotatable roller. It is preferably applied in athin coat with a thickness of between 1 and 100 μ. This coat thicknessdefines the maximum thickness of the pigments in the subsequent grindingprocess and also facilitates the grinding of the coat into plateletlikepigments. These plateletlike pigments are able to arrange themselvesuniformly in thin coating films to give a uniform perceived color.

Liquid crystals with twisted cholesteric phases develop their opticalproperties only when the individual molecules are aligned in a helicalsuperstructure. The formation of this superstructure occurs to someextent spontaneously, while in some cases the orientation has to beinduced by the action of external forces.

Following application, therefore, the liquid-crystalline compounds areoriented in the coat. This is achieved most simply by means of the shearforces which act during application. However, orientation can also beeffected by other known methods, such as knife coating, alignment layersor, for some liquid-crystalline systems, by means of electrical ormagnetic fields.

Following orientation, the ordered liquid-crystalline state obtained isfixed by polymerization. Particularly favorable forms of polymerizationin this context are those induced by light or electron beams, since theycan be carried out regardless of temperature. Indeed, the temperature isa not unimportant parameter for the helical pitch of the liquid crystaland thus for the color of the interference effect and should thereforeadvantageously, as a color design parameter, not be restricted by thepolymerization conditions.

Following polymerization, the hardened liquid-crystal coat is detachedfrom the surface and comminuted by known methods until the desiredpigment particle size is reached.

In the novel process the polymerizable mixture comprises not onlyliquid-crystalline monomeric compounds, with or without chiral dopants,but also a polymeric binder and/or monomeric compounds which can beconverted into a polymeric binder by polymerization, and/or a dispersionauxiliary. Even in small amounts these substances increase the flowviscosity of the liquid-crystal phase and substantially facilitate theorientation of the liquid-crystal molecules. Because of the facilitatedorientation, complex orientation methods become unnecessary andorientation occurs usually spontaneously by means of the coatingoperation. In addition, a more uniform orientation is achieved, which ismanifested in increased brightness of color of the coats and of thepigments.

Examples of suitable polymeric binders are soluble (in organic solvents)polyesters, cellulose esters, polyurethanes, silicones and polyether- orpolyester-modified silicones. Particular preference is given to the useof cellulose esters such as cellulose acetobutyrate. Even small amountsof such substances--usually just 0.1 to 1% by weight--bring about aconsiderable improvement in the flow viscosity. At the same time, thesesubstances have a great influence on the mechanical properties of thehardened pigment particles.

Other particularly suitable polymeric binders are those comprisingreactive crosslinkable groups, such as acrylic, methacrylic,α-chloroacrylic, vinyl, vinyl ether, epoxide, cyanate, isocyanate orisothiocyanate groups. Monomeric substances are also suitable asbinders, especially the reactive diluents known from paint preparationsuch as, for example, hexanediol diacrylate or bis-phenol A diacrylate.

Dispersion auxiliaries as well have a positive effect on the flowviscosity of the polymerizable mixture, on the miscibility of theindividual components and on the orientation of the liquid crystals. Asdispersion auxiliaries it is possible to employ all commerciallyavailable substances.

Particularly suitable dispersion auxiliaries are those based on asuccinimide, succinate or succinic anhydride structure, as described inprior German Patent Application 19 532 419.6.

Among these dispersion auxiliaries, particular preference is given tothe derivatives of polyisobutylenesuccinic acid.

As the cholesteric liquid-crystalline component the polymerizablemixture can comprise either

a₁) at least one chiral liquid-crystalline polymerizable monomer or

a₂) at least one achiral liquid-crystalline polymerizable monomer and achiral compound.

As component a₁) the polymerizable mixture preferably comprises monomersof the general formula I ##STR1## where

Z¹ is a polymerizable group or a radical which carries a polymerizablegroup,

Y¹, Y², Y³ are chemical bonds, oxygen, sulfur, --CO--O--, --O--CO--,--O--CO--O--, --CO--N(R)-- or --N(R)--CO--,

A¹ is a spacer,

M¹ is a mesogenic group,

X is an n-valent chiral radical,

R is hydrogen or C_(l) -C₄ -alkyl, and

n is 1 to 6,

it being possible for the radicals Z¹, Y¹, Y², Y³, A¹ and M¹ to beidentical or different.

Preferred radicals Z¹ are: ##STR2## in which R is identical or differentat each occurrence and is hydrogen or C₁ -C₄ -alkyl, eg. methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Amongthe reactive polymerizable groups, the cyanates are able to trimerizespontaneously to form cyanurates and are therefore mentioned withpreference. The other groups mentioned require further compounds withcomplementary reactive groups for polymerization. For example,isocyanates can polymerize with alcohols to form urethanes and withamines to form urea derivatives. Similar comments apply to thiiranes andaziridines. Carboxyl groups can be condensed to form polyesters andpolyamides. The maleimido group is particularly suitable forfree-radical copolymerization with olefinic compounds such as styrene.In this context, the complementary reactive groups can be present eitherin a second compound according to the invention, which is mixed with thefirst, or can be incorporated into the polymeric network by auxiliarycompounds comprising two or more such complementary groups.

Particularly preferred groups Z¹ -Y¹ are acrylate and methacrylate.

Y¹ -Y³ can be as defined above, the term chemical bond being intended todenote a single covalent bond.

Suitable spacers A¹ are all groups known for this purpose. The spacersgenerally contain 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms,and consist of linear aliphatic groups. Their chain can be interrupted,for example, by O, S, NH or NCH₃, but these groups cannot be adjacent.Suitable substituents for the spacer chain are fluorine, chlorine,bromine, cyano, methyl and ethyl.

Examples of representative spacers are: ##STR3## where

m is 1 to 3 and

p is 1 to 12.

The mesogenic group M¹ preferably has the structure

    (T-Y.sup.8).sub.s -T

where Y⁸ is a bridge member conforming to one of the definitions of Y¹,s is 1 to 3 and each T, independently at each occurrence, is a divalentisocycloaliphatic, heterocycloaliphatic, isoaromatic or heteroaromaticradical.

T can also be a ring system substituted by fluorine, chlorine, bromine,cyano, hydroxyl or nitro; preferred radicals T are: ##STR4##

The following mesogenic groups M¹ are particularly preferred: ##STR5##

For reasons including that of availability, particularly preferredchiral radicals X of the compounds of the general formula I are thosederived from sugars, from binaphthyl or biphenyl derivatives and fromoptically active glycols, dialcohols or amino acids. Notable sugars are,in particular, pentoses and hexoses and their derivatives.

Examples of radicals X are the following structures, the lines at theend in each case denoting the free valences. ##STR6##

Particular preference is given to ##STR7##

Also suitable are chiral groups having the following structures:##STR8##

Further examples are given in German Application P 43 42 280.2.

n is preferably 2.

As component a₂) the polymerizable mixture in the novel processpreferably comprises at least one achiral liquid-crystallinepolymerizable monomer of the general formula II

    Z.sup.2 -Y.sup.4 -A.sup.2 -Y.sup.5 -M.sup.2 -Y.sup.6 -A.sup.3 -Y.sup.7 -Z.sup.3                                                  II

where

Z² and Z³ are polymerizable groups or radicals containing apolymerizable group,

Y⁴, Y⁵,Y⁶, Y⁷ are chemical bonds, oxygen, sulfur, --CO--O--, --O--CO --,--O--CO--O--, --CO--N(R)-- or --N(R)--CO--,

A² and A³ are spacers, and

M² is a mesogenic group.

In this context, the polymerizable groups, the bridge members Y⁴ to Y⁷,the spacers and the mesogenic group are subject to the same preferencesas the corresponding variables in the general formula I.

Component a₂) additionally comprises a chiral compound. The chiralcompound brings about the twisting of the achiral liquid-crystallinephase to form a cholesteric phase. In this context, the extent oftwisting depends on the twisting capacity of the chiral dopant and onits concentration. Consequently, therefore, the pitch of the helix and,in turn, the interference color are also dependent on the concentrationof the chiral dopant. As a result, it is not possible to state agenerally valid concentration range for the dopant. The dopant is addedin the amount which produces the desired color effect.

Preferred chiral compounds are those of the formula Ia

     Z.sup.1 -Y.sup.1 -A.sup.1 -Y.sup.2 -M.sup.a -Y.sup.3 -!.sub.n XIa,

where Z¹, Y¹, Y², Y³, A¹, X and n are as defined above and M^(a) is adivalent radical containing at least one heterocyclic or isocyclic ringsystem.

In this formula the molecular subunit M^(a) resembles the mesogenicgroups described, since in this way particularly good compatibility withthe liquid-crystalline compound is achieved. However, M^(a) need notactually be mesogenic, since the compound Ia is intended to bring aboutan appropriate twisting of the liquid-crystalline phase solely by meansof its chiral structure. Preferred ring systems present in M^(a) are theabovementioned structures T, and preferred structures M^(a) are those ofthe above formula (T-Y⁸)_(s) -T.

The pigments prepared in accordance with the invention have particularproperties in respect of their brightness of color. The epithet novel istherefore considered to apply to all those pigments as are obtainable bythe process described.

A further advantage of the novel pigments is their relatively narrowsize distribution. Application of the polymerizable mixtures to asurface produces highly uniform coats, which is manifested subsequentlyin a narrower range of scatter of the thickness of the ground pigmentparticles. In surface coating compositions, these pigments exhibitbetter orientation and a smoother surface.

The novel pigments can be incorporated into various coatingcompositions, which comprise

one or more novel pigments,

one or more customary paint binders,

if desired, further pigments or dyes,

if desired, one or more crosslinkers, and

if desired, customary paint additives and/or fillers.

Examples of customary paint binders which can be present in the coatingcompositions are polyesters, alkyd resins, polyurethanes, (meth)acryliccopolymers and cellulose ester-based resins. These binders may bedispersed or dissolved in organic solvents.

Further pigments which can be present are any desired organic and/orinorganic pigments as are customarily employed in coating materials.Examples of such pigments are titanium dioxide, iron oxide, carbonblack, azo pigments, phthalocyanine pigments, perylene pigments,quinacridone pigments or pyrrolopyrrole pigments.

Other suitable plateletlike special-effect pigments are the customarymetal pigments, for example those of aluminum or copper, and the metaloxide-coated metallic pigments, other special-effect pigments, forexample pearl luster (pearlescent) and interference pigments, forexample coated mica, metal oxide-coated aluminum, nitrotitanium dioxideand graphite effect pigments, plateletlike (micaceous) iron oxide,molybdenum disulfide pigments, plateletlike copper phthalocyaninepigments, bismuth oxychloride platelets and coated glass flakes. Themixed oxide-coated aluminum and mica pigments can be coated with organicpigments.

Crosslinked or noncrosslinked polymer microparticles customary in paintscan also be present in the coating composition.

Fillers which may be present are all those which are customary in theformulation of paints. Preference is given to silica, barium sulfate andtalc.

Dyes which can be present in the coating composition are all those whichare customary in the formulation of paints. Preferred dyes are thosehaving one of the interference colors.

Examples of crosslinkers which can be present in the coating compositionare formaldehyde condensation resins, such as phenol-formaldehyde andamine-formaldehyde condensation resins or polyisocyanates. The reactivediluents already mentioned above can also be added as crosslinkers.

As customary paint additives the coating compositions may comprise alladditives familiar to the person skilled in the art, such as highlydisperse silica, phyllosilicates, polymeric urea compounds, celluloseethers such as hydroxyethylcellulose, methylcellulose,carboxymethylcellulose, polyvinyl alcohol, poly(meth)acrylates andpoly(meth)acrylamides, polyvinylpyrrolidone and other hydrophilic andhydrophobic polymers and copolymers, flow aids, light stabilizers,antifoams, wetting agents and adhesion promoters.

Other suitable customary paint additives are polymerization initiatorsand polymerization catalysts.

The coating compositions can also comprise one or more organic solvents.Examples of suitable solvents are mono- or polyhydric alcohols such aspropanol, butanol and hexanol, glycol ethers and glycol esters, such asdiethylene glycol dialkyl ethers, glycols, such as ethylene glycol orpropylene glycol, ketones, such as methyl ethyl ketone or acetone,esters, such as ethyl acetate and butyl acetate, and aromatic andaliphatic hydrocarbons.

Preferred coating compositions are those comprising water as diluent. Inthese aqueous coating compositions there are water-compatible bindersand additives as are familiar to the person skilled in the art. Forinstance, water-soluble binders having anionic or cationic groups areused for these coating compositions.

Preference is given to anionically stabilized binders based onpolyesters, (meth)acrylic copolymers or, with particular preference,polyurethanes.

Particular preference is given to the use of the novel pigments as aconstituent of two-coat systems of the basecoat-clearcoat type, as havebecome established for effect finishes.

Basecoat/clearcoat systems are prepared by first of all applying apigmented basecoat, preferably a dark-pigmented basecoat, and thenovercoating the basecoat, preferably by a wet-on-wet method, i.e. aftera short flash-off time without a baking step, for example at 20-80° C.,with a customary clearcoat in a dry-film thickness of 30-80 μm, and thendrying or crosslinking basecoat and clearcoat together at 20-140° C.

The drying conditions for the topcoat layer (basecoat and clearcoat)depend on the clearcoat system used. OEM (production-line) finishinggenerally employs more than 80° C. for two-component clearcoats,preferably more than 120° C. for one-component clearcoats. Refinishesproduced with polyisocyanate-based two-component clearcoats are cured atroom temperature or at no more than 80° C.

Suitable clearcoats are all customary clearcoats ortransparent-pigmented clearcoats or tinted clearcoats.

Those which are particularly suitable areconventional/solvent-containing one- or two-component high-solidscoatings, water-dilutable clearcoats or transparent powder coatings.

The novel pigments are preferably used in inks, including printing inks,and in emulsion paints and other surface coatings.

The novel coating compositions are particularly suitable for coating,especially painting, substrates. Substrates which can be used includemetallic, paper, wood or plastics substrates. They are frequentlyprecoated or preprinted.

Customary forms of precoating for metallic substrates are zincphosphatization, electrodeposition coating and, if desired, one or moresprayed coats, for example a primer-surfacer coat or else a solid-color(strait-shade) basecoat or topcoat.

These coats are in general fully cured. Dark pigmented coats arepreferred. Plastics substrates can be provided with a plastics primer,preferably a dark plastics primer.

The novel coating compositions are particularly suitable for coating orpainting commodity articles. The color effects on jewelry, packagingmaterial, bottles, domestic articles and, in particular, on vehiclessuch as bicycles, motorbikes, and especially motor cars, have appearedto be of particular interest.

EXAMPLE 1

Preparation of cholesteric liquid-crystalline pigments comprisingcellulose acetobutyrate

A polymerizable mixture was prepared from

7.9% by weight of each of the following liquid-crystalline monomers:##STR9## (The preparation of the monomers is described in prior GermanPatent Application 19 532 408.0),

4.5% by weight of the following chiral dopant ##STR10## (The preparationof the dopant is described in prior German Patent Application P 43 42280.2),

1.9% by weight of a commercial polymerization initiator (Lucirin® TPO,manufacturer BASF, Ludwigshafen),

0.6% by weight of cellulose acetobutyrate, and

19.9% by weight of tetrahydrofuran.

(The percentages by weight relate to the overall quantity of thepolymerizable mixture.)

The mixture was applied to a glass substrate using a spiral doctor blade(coat thickness 4 μm). After evaporation of the solvent, the mixture waspolymerized using UV light (wavelength 360 nm, 160 W/cm). The cured coatwas detached mechanically from the substrate and ground in an analyticalmill (model A10, IKA) and the ground material was separated by means ofa sieve set. The resulting pigment particles had a maximum diameter ofabout 80 μm and a thickness of from 4 to 6 μm.

EXAMPLE 2

Comparison example: Preparation of cholesteric liquid-crystallinepigments without cellulose acetobutyrate.

Pigments were prepared by the method of Example 1 without celluloseacetobutyrate. The resulting pigment particles have a maximum diameterof 80 μm and a wider scatter of the thickness, from about 4 to 50 μm.

EXAMPLE 3

Preparation of the novel coating compositions

10% by weight of the pigments described in Example 1 were formulatedwith 90% by weight of a commercial nonpigmented basecoat based onsaturated polyesters, cellulose derivative and amino resins to form ahomogeneous mixture.

This mixture was adjusted to a spray viscosity of 18 seconds DIN4 with amixture of 50% by volume of butyl acetate and 50% by volume of xylene.The solids content of the basecoat was 20% by weight.

The paint had a bright color with a reflection wavelength of 530 nm anda strongly pronounced color flop. The surface was homogeneous.

EXAMPLE 4

Comparison example: Coating composition with pigments from Example 2.

A coating film was prepared as in Example 3 from the pigments ofComparison Example 2. The perceived color of the coat was less bright,and its surface was rather rough.

EXAMPLE 5

Preparation of a multicoat finish of the basecoat/clearcoat type

a) Clearcoats used

The OEM clearcoat used was the commercial stoving enamel (FF92-0130,BASF L+F AG) based on acrylic resin, amino resin.

The refinish clearcoat used was a commercial two-component high-solidsGlassodur clearcoat (923-54) with two-component high-solids Glassodurhardener (929-71) and diluent (352-91) from BASF L+F AG.

b) Preparation of the two-coat finish

The coating composition prepared in Example 3 was applied to aconventionally zinc phosphatized, electrocoated and sprayedprimer-pretreated metal panel, using a compressed-air atomizing spraygun, so as to give an overall dry-film thickness of 15 to 30 μm.Application took place at an ambient temperature of 23° C. and at 60%relative atmospheric humidity.

After applying the basecoat, it was flashed off at ambient temperaturefor 30 minutes and then overcoated with the abovedescribed clearcoats.

Stoving was carried out at 130° C. for 30 minutes for the one-componentOEM clearcoat and at 80° C. for 20 minutes for the two-componentrefinish clearcoat.

We claim:
 1. A process for preparing pigments comprising applying apolymerizable mixture to a surface, orienting liquid crystals present inthe mixture, polymerizing the mixture, detaching a polymer film formedfrom the mixture from the surface and comminuting the polymer film toform pigment particles, wherein the polymerizable mixture comprises:a₁)at least one chiral liquid-crystalline polymerizable monomer or a₂) atleast one achiral liquid-crystalline polymerizable monomer and a chiralcompound, and additionally b) (1) a polymeric binder and/or (2)monomeric compounds which can be converted by polymerization into apolymeric binder and/or (3) a dispersion auxiliary.
 2. A process asclaimed in claim 1, wherein a polymeric binder is employed as componentb).
 3. The process as claimed in claim 2, wherein the polymeric binderemployed is cellulose acetobutyrate.
 4. The process as claimed in claim1, wherein a dispersion auxiliary is employed as component b).
 5. Aprocess as claimed in claim 4, wherein the dispersion auxiliary employedis a polyisobutylene succinic acid derivative.
 6. A process as claimedin claim 1, wherein component a₁) comprises at least one chiralliquid-crystalline polymerizable monomer of the general formula I

     Z.sup.1 -Y.sup.1 -A.sup.1 -Y.sup.2 -M.sup.1 -Y.sup.3 -!.sub.n XI

where Z¹ is a polymerizable group or a radical which carries apolymerizable group, Y¹, Y², Y³ are chemical bonds, oxygen, sulfur, --CO--O--, --O--CO--, --O--CO --O--, --CO--N(R)-- or --N(R)--CO--, A¹ is aspacer, M¹ is a mesogenic group, X is an n-valent chiral radical, R ishydrogen or C₁ -C₄ -alkyl, and n is 1 to 6,it being possible for theradicals Z¹, Y¹, Y², Y³, A¹ and M¹ to be identical or different.
 7. Aprocess as claimed in claim 1, wherein component a₂) comprises at leastone achiral liquid-crystalline polymerizable monomer of the generalformula II

    Z.sup.2 -Y.sup.4 -A.sup.2 -Y.sup.5 -M.sup.2 -Y.sup.6 -A.sup.3 -Y.sup.7 -Z.sup.3                                                  II

where Z² and Z³ are polymerizable groups or radicals containing apolymerizable group, Y⁴, Y⁵, Y⁶, Y⁷ are chemical bonds, oxygen, sulfur,--CO--O--, --O--CO--, --O--CO--O--, --CO--N(R)-- or --N(R)--CO--, A² andA³ are spacers, and M² is a mesogenic group.
 8. A process as claimed inclaim 1, wherein component a₂) comprises a chiral compound of thegeneral formula Ia

     Z.sup.1 -Y.sup.1 -A.sup.1 -Y.sup.2 -M.sup.a -Y.sup.3 -!.sub.n XIa

where Z¹ is a polymerizable group or a radical which carries apolymerizable group, Y¹, Y², Y³ are chemical bonds, oxygen, sulfur,--CO--O--, --O--CO--, --O--CO --O--, --CO--N(R)-- or --N(R)--CO--, R ishydrogen or C₁ -C₄ alkyl, A¹ is a spacer, X is an n-valent chiralradical, n is 1 to 6, and M^(a) is a divalent radical containing atleast one heterocyclic or isocyclic ring system,and wherein Z¹, Y², Y²,Y³, A¹, and M^(a) are the same or different.
 9. A pigment obtained bythe process as claimed in claim
 1. 10. A coating compositioncomprisingone or more pigments as claimed in claim 9, one or morecustomary paint binders, optionally, further pigments or dyes,optionally, one or more crosslinkers, and optionally, customary paintadditives and/or fillers.
 11. A coating composition as claimed in claim10, comprising as customary paint binders those based on polyesters,alkyd resins, polyurethanes, (meth)acrylic copolymers and/or celluloseesters.
 12. A coating composition as claimed in claim 10, comprising ascustomary paint binders water-dilutable, anionically stabilized resins.13. An ink or surface coating comprising the pigment as claimed in claim9.
 14. An emulsion paint comprising the pigment as claimed in claim 9.15. A method comprising applying the coating composition as claimed inclaim 10 on a commodity article.
 16. A method comprising painting avehicle with the coating composition as claimed in claim
 10. 17. Avehicle coated with a coating composition as claimed in claim 10.